Process for producing olefin polymers using cationic catalysts

ABSTRACT

A cationic catalyst composition comprising a reactive cation and a compatible non-coordinating anion used at a temperature of 20 DEG  C. or less to produce olefin polymers, particularly polyisobutylene is disclosed.

FIELD OF THE INVENTION

This invention relates to a method for the cationic polymerization ofolefins using catalysts comprising a cation and a compatiblenon-coordinating anion. This invention further relates to the use ofcomplexes containing a compatible non-coordinating anion to initiatecationic polymerization.

BACKGROUND OF THE INVENTION

The cationic polymerization of olefins is typically conducted in thepresence of catalyst systems comprising a Lewis acid, a tertiary alkylinitiator molecule containing a halogen, ester, ether, acid or alcoholgroup and occasionally an electron donor molecule such as ethyl acetate.The exact combination of the components varies with each system. Thetertiary alkyl initiators used in these systems are used for living andnon-living carbocationic catalysts. The tertiary alkyl initiators aretypically represented by the formula: ##STR1## wherein R₁, R₂, and R₃are a variety of alkyl or aromatic groups or combinations thereof, n isthe number of initiator molecules and X is the functional group on whichthe Lewis acid affects a change to bring about the carbocationicinitiating site. This group is typically a halogen, ester, ether,alcohol or acid group depending on the Lewis acid employed. One or twofunctional groups per initiator tend to lead to linear polymers whilethree or more tend to lead to star polymers.

Catalyst systems based on halogens and/or alkyl containing Lewis acids,such as boron trichloride and titanium tetrachloride, use variouscombinations of the above components and typically have similar processcharacteristics. For living polymerization systems, Lewis acidconcentrations must exceed the concentration of initiator sites by 16 to40 times in order to achieve 100 percent conversion in 30 minutes (basedupon a degree of polymerization equal to 890) at -75 to -80° C.

In nonliving polymerizations, high molecular weight polyisobutylenes areonly prepared at low temperatures (-60 to -100° C.) and at catalystconcentrations exceeding one catalyst molecule per initiator molecule.Frequently, these catalysts are restricted in their use to certainnarrow temperature regions and concentration profiles. An improvedcatalyst could be used stoichiometrically rather than in excess toprovide enough initiation sites over a wide range of temperatureswithout affecting its suitability.

Furthermore a new class of catalysts utilizing compatiblenon-coordinating anions in combination with cyclopentadienyl transitionmetal compounds has recently been disclosed by Turner and Hlatkey inU.S. Ser. Nos., 542,235, filed Jun. 22, 1990; U.S. Pat. No. 5,153,157;U.S. Pat. No. 5,198,401; and European Patent Applications 520 732,published Dec. 20, 1992; 277 003 & 277 004, each published Jun. 3, 1988.This system polymerizes olefins using a coordination mechanism innon-polar solvents. U.S. Pat. Nos. 5,196,490, 5,066,741 and 4,808,680disclose the preparation of syndiotactic polystyrene or vinyl aromaticsusing non-coordinating anions in combination with cyclopentadienyltransition metal derivatives at coordination catalysis conditions.

It is desirable that a new catalyst system utilizing compatiblenon-coordinating anions in polar or non-polar solvent be produced thatcan polymerize olefins heretofore only polymerizable by cationiccatalyst as well as typical monomers polymerized by coordinationcatalysis, preferably at the same time.

SUMMARY OF THE INVENTION

This invention relates in part to the discovery that a non-coordinatinganion can be combined with different compositions to form cationicpolymerization catalyst systems. In addition this invention furtherrelates to the discovery that monomer choice will typically determinethe reaction mechanism (coordination versus cationic) for catalystsystems comprising a cyclopentadienyl transition metal derivative and acompatible non-coordinating anion.

Therefore, in accordance with this invention, there is provided acationic polymerization catalyst system, a method for cationicpolymerization using a catalyst system which comprises a compatiblenon-coordinating anion. Another aspect of the invention is directedtoward certain novel catalyst systems for cationic polymerization and amethod of using this catalyst system for the polymerization ofcationically polymerizable olefins. A particularly desirable aspect isthe polymerization by both coordination mechanism and cationic mechanismat the same time.

DESCRIPTION OF THE FIGURES

FIG. 1 is a ¹ H-NMR of Fraction C of sample 158-3.

FIG. 2 is a ¹ H-NMR of Fraction 4 of samples 158-3 & 158-1.

DESCRIPTION OF PREFERRED EMBODIMENTS

This invention relates to a method for cationic polymerization whichutilizes a catalyst composition comprising a reactive cation and acompatible non-coordinating anion. The catalyst composition comprisingthe compatible non-coordinating anion will include a reactive cation andin certain instances are novel catalyst systems. A reactive cation isany cation that can react with an olefin to create a carbocationicpolymerization site.

A "compatible non-coordinating anion," (hereinafter "NCA") is defined tobe an anion which either does not coordinate the cation or which is onlyweakly coordinated to the cation thereby remaining sufficiently labileto be displaced by an olefin monomer. Further the phrase "compatiblenon-coordinating anion" specifically refers to an anion which whenfunctioning as a stabilizing anion in the catalyst systems of thisinvention does not irreversibly transfer an anionic substituent orfragment thereof to the cation thereby forming a neutral by product orother neutral compound. Compatible non-coordinating anions are anionswhich are not degraded to neutrality when the initially formed complexdecomposes. Preferred examples of such compatible non-coordinatinganions include: alkyltris(pentafluorophenyl) boron (RB(pfp)₃ ⁻),tetraperfluorophenylboron (B(pfp)₄ ⁻), tetraperflourophenylaluminum,carboranes, halogenated carboranes and the like. Hereinafter the use ofthe phrase NCA or non-coordinating anion means the compatiblenon-coordinating anions described above.

This catalyst system can be used, among other things, for the cationicpolymerization of olefins, especially traditional cationicallypolymerizable olefins, particularly geminally disubstituted olefins.Certain of these catalyst systems can also be used to polymerize bothcationically polymerizable monomers and typical coordinationpolymerizable monomers.

For ease of description the formulae presented below depict the catalystcomponents in the "ionic" state. One of ordinary skill in the art willrealize that many of these components are not stable as depicted and areobtained from a neutral stable form. For example. ##STR2## typicallydoes not exist in this state. (Rather it is formed by reacting Cp₂ ZrMe₂with another compound that will abstract an Me group.) This conventionof describing the components in "ionic" form is used for descriptivepurposes only and should not be construed as limiting in any way.

For lists describing the neutral stable forms of the cyclopentadienyltransition metal compositions and the NCA see European PatentApplication ("EPA") 129 368, published Dec. 27, 1984; U.S. Pat. No.5,055,438; U.S. Ser. No. 07/542,235, filed Jun. 22, 1990; EPA 520 732,published Dec. 30, 1992; U.S. Pat. No. 5,017,714; U.S. Pat. No.5,198,401; U.S. Pat. No. 5,153,157; EPA 277 003 and 277 004, publishedAug. 5, 1992, all of which are incorporated by reference herein. It hasbeen noted however, that the analinium containing compounds have aninhibiting effect on the carbocationic polymerization.

For lists describing the neutral stable forms of the substitutedcarbocations see U.S. Pat. No. 4,910,321; U.S. Pat. No. 4,929,683; andEPA 341 012. In general the neutral stable form is typically representedby the formula: ##STR3## wherein R₁, R₂, and R₃ are a variety of alkylor aromatic groups or combinations thereof, n is the number of initiatormolecules and is preferably greater than or equal to 1, even morepreferably between 1 and 30, and X is the functional group on which theLewis acid affects a change to bring about the carbocationic initiatingsite. This group is typically a halogen, ester, ether, alcohol or acidgroup depending on the Lewis acid employed.

For a description of stable forms of the substituted silylium, see F. A.Cotton, G. Wilkinson, Advanced Inorganic Chemistry, John Wiley and Sons,New York 1980. Likewise for stable forms of the cationic tin, germaniumand lead compositions see Dictionary of organometallic compounds,Chapman and Hall New York 1984.

Catalyst System

General Description

Catalyst systems of this invention generally comprise two components: areactive cation and a campatible non-coordinating anion. The anion maybe combined with the cation by any method known to those of ordinaryskill in the art. For example, a composition containing the NCA fragmentis first treated to produce the anion in the presence of the reactivecation or reactive cation source, i.e. the anion is activated. Likewisethe NCA may be activated without the presence of the reactive cation orcation source which is subsequently introduced. In a preferredembodiment a composition containing the anion and a compositioncontaining the reactive cation are combined and allowed to react to forma by product, the anion and the cation. In another preferred embodimentthe NCA is introduced into the solvent as a compound containing both theanion and the cation in the form of the active catalyst system.

Non-Coordinating Anions

A preferred class of compatible non-coordinating anions includeschemically stable, non-nucleophilic substituted anionic complexes havinga molecular diameter of about 4 Angstroms or more.

Any metal or metalloid compound capable of forming an anionic complexwhich is resistant to irreversibly transferring a substituent orfragment to the cation to neutralize the cation to produce a neutralmolecule may be used as the NCA. In addition any metal or metalloidcapable of forming a coordination complex which is stable in water mayalso be used or contained in a composition comprising the anion.Suitable metals include, but are not limited to aluminum, gold, platinumand the like. Suitable metalloids include, but are not limited to,boron, phosphorus, silicon and the like. Compounds containing anionswhich comprise coordination complexes containing a single metal ormetalloid atom are, of course, well known and many, particularly suchcompounds containing a single boron atom in the anion portion, areavailable commercially. In light of this, salts containing anionscomprising a coordination complex containing a single boron atom arepreferred.

In general, preferred NCAs may be represented by the following generalformula:

    [(M').sup.m+ Q.sub.1 . . . Q.sub.n ].sup.d-

wherein:

M' is a metal or metalloid;

Q₁ to Q_(n) are, independently, bridged or unbridged hydride radicals,dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl andsubstituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbylradicals and hydrocarbyl and halocarbyl-substituted organometalloidradicals and any one, but not more than one of Q₁ to Q_(n) may be ahalide radical;

m is an integer representing the formal valence charge of M;

n is the total number of ligands Q, and

d is an integer greater than or equal to 1.

It is of course understood that the anions described above and below maybe counter balanced with a positively charged component that is removedbefore the anion acts with the cation.

In a preferred embodiment M' is boron, n=4, Q₁ and Q₂ are the same ordifferent aromatic or substituted-aromatic hydrocarbon radicalscontaining from about 6 to about 20 carbon atoms and may be linked toeach other through a stable bridging group; and

Q₃ and Q₄ are, independently, hydride radicals, hydrocarbyl andsubstituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbylradicals, hydrocarbyl- and halocarbyl-substituted organometalloidradicals, disubstituted pnictogen radicals, substituted chalcogenradicals and halide radicals, with the proviso that Q₃ and Q₄ will notbe halide at the same time.

Illustrative, but not limiting, examples of boron components which maybe used as NCAs are: tetra-valent boron compounds such astetra(phenyl)boron, tetra(p-tolyl)boron, tetra(o-tolyl)boron,tetra(pentafluorophenyl)boron, tetra(o,p-dimethylphenyl)boron,tetra(m,m-dimethylphenyl)boron, (p-tri-fluoromethylphenyl)boron and thelike.

In a particularly preferred embodiment M=boron, n=4, Q₁, Q² and Q₃ areeach (C₆ F₅) and Q₄ is as defined above. Illustrative but not limiting,examples of these preferred NCAs comprising boron triphenylmethyl saltswhere Q is a simple hydrocarbyl such as methyl, butyl, cyclohexyl, orphenyl or where Q is a polymeric hydrocarbyl of indefinite chain lengthsuch as polystyrene, polyisoprene, or poly-paramethylstyrene.

Another preferred class of NCAs is that class comprising those NCAcontaining a plurality of boron atoms, including boranes and carboranes.

Illustrative, but not limiting, examples of NCAs include:

carboranes such as dodecaborate, decachlorodecaborate,dodecachlorododecaborate, 1-carbadecaborate, 1-carbadecaborate,1-trimethylsilyl-1-carbadecaborate;

Borane and carborane complexes and salts of borane and carborane anionssuch as decaborane(14), 7,8-dicarbadecaborane(13),2,7-dicarbaundecaborane(13),undecahydrido-7,8-dimethyl-7,8-dicarbaundecaborane,6-carbadecaborate(12), 7-carbaundecaborate, 7,8-dicarbaudecaborate; and

Metallaborane anions such asbis(nonahydrido-1,3-dicarbanonaborato)cobaltate(III),bis(undecahydrido-7,8-dicarbaundecaborato) ferrate(III),bis(undecahydrido-7,8-dicarbaundecaborato) cobaltate(III),bis(undecahydrido-7,8-dicarbaunaborato) nikelate(III),bis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborato)ferrate(III),bis(tribromooctahydrido-7,8-dicarbaundecaborato)cobaltate(III),bis(undecahydridodicarbadodecaborato) cobaltate(III) andbis(undecahydrido-7-carbaundecaborato) cobaltate(III).

The NCA compositions most preferred for forming the catalyst system usedin this process are those containing a tris-perfluorophenyl boron,tetrapentafluorphenyl boron anion and/or two or moretripentafluorophenyl boron anion groups covalently bond to a centralatomic molecular or polymeric complex or particle.

Cationic Component

In various preferred embodiments of this invention the NCA is combinedwith one or more cations that are selected from different classes ofcations and cation sources.

Some preferred classes are:

(A) cyclopentadienyl transition metal complexes and derivatives thereof.

(B) a substituted carbocation whose composition is represented by theformula: ##STR4## wherein R₁, R₂ and R₃ are hydrogen, alkyl, aryl,aralkyl groups or derivatives thereof, preferably C₁ to C₃₀ alkyl, aryl,aralkyl groups or derivatives thereof, provided that only one of R₁, R₂and R₃ may be hydrogen at any one time;

(C) substituted silylium; preferably those represented by the formula:##STR5## wherein R₁, R₂ and R₃ are hydrogen, alkyl, aryl, aralkyl groupsor derivatives thereof, preferably C₁ to C₃₀ alkyl, aryl, aralkyl groupsor derivatives thereof, provided that only one of R₁, R₂ and R₃ may behydrogen at any one time;

(D) compositions capable of generating a proton; and

(E) cationic compositions of germanium, tin or lead, some of which arerepresented by the formula: ##STR6## wherein R₁, R₂ and R₃ are hydrogen,alkyl, aryl, aralkyl groups or derivatives thereof, preferably C₁ to C₃₀alkyl, aryl, aralkyl groups or derivatives thereof, and M* is Ge, Sn orPb, provided that only one of R₁, R₂ and R₃ may be hydrogen at any onetime.

A. Cyclopentadienyl Metal Derivatives

Preferred cyclopentadienyl transition metal derivatives includetransition metals that are a mono-, bis- or tris- cyclopentadienylderivative of a Group 4, 5 or 6 transition metal, preferably amono-cyclopentadienyl (Mono-Cp) or bis-cyclopentadienyl (Bis-Cp) Group 4transition metal compositions, particularly a zirconium, titanium orhafnium compositions.

Preferred cyclopentadienyl derivatives (cation sources) that may becombined with non-coordinating anions are represented by the followingformulae: ##STR7## wherein: (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*;

Cp and Cp* are the same or different cyclopentadienyl rings substitutedwith from zero to five substituent groups S, each substituent group Sbeing, independently, a radical group which is a hydrocarbyl,substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen or halogen radicals, or Cp and Cp* arecyclopentadienyl rings in which any two adjacent S groups are joinedforming a C₄ to C₂₀ ring system to give a saturated or unsaturatedpolycyclic cyclopentadienyl ligand;

R is a substituent on one of the cyclopentadienyl radicals which is alsobonded to the metal atom;

A' is a bridging group, which group may serve to restrict rotation ofthe Cp and Cp* rings or (C₅ H_(5-y-x) S_(x)) and JR' .sub.(z-1-y)groups;

M is a Group 4, 5, or 6 transition metal;

y is 0 or 1;

(C₅ H_(5-y-x) S_(x)) is a cyclopentadienyl ring substituted with fromzero to five S radicals;

x is from 0 to 5 denoting the degree of substitution;

JR' .sub.(z-1-y) is a heteroatom ligand in which J is a Group 15 elementwith a coordination number of three or a Group 16 element with acoordination number of 2, preferably nitrogen, phosphorus, oxygen orsulfur;

R" is a hydrocarbyl group, preferably an alkyl group;

X and X₁ are independently a hydride radical, hydrocarbyl radical,substituted hydrocarbyl radical, halocarbyl radical, substitutedhalocarbyl radical, and hydrocarbyl- and halocarbyl-substitutedorganometalloid radical, substituted pnictogen radical, or substitutedchalcogen radicals; and

L is an olefin, diolefin or aryne ligand, or a neutral Lewis base.

Additional cyclopentadienyl compounds that may be used in this inventionare described in U.S. patent application Ser. Nos. 133,480; and 542,236,and U.S. Pat. Nos. 5,055,438, 5,278,119, 5,198,401 and 5,096,867, whichare incorporated by reference herein.

B. Substituted Carbocation Cations

Another preferred source for the cation is substituted carbocations.Preferred examples include substances that are represented by theformula: ##STR8## wherein R₁, R₂ and R₃ are independently hydrogen, or alinear, branched or cyclic aromatic or aliphatic groups, preferably a C₁to C₂₀ aromatic or aliphatic group, provided that only one of R₁, R₂ orR₃ may be hydrogen. In a preferred embodiment none of R₁, R₂ or R₃ areH. Preferred aromatics include phenyl, toluyl, xylyl, biphenyl and thelike. Preferred aliphatics include methyl, ethyl, propyl, butyl, pentyl,hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl,3,5,5-trimethylhexyl and the like. In a particularly preferredembodiment, when R₁, R₂ and R₃ are phenyl groups, the addition of analiphatic or aromatic alcohol significantly enhances the polymerizationof isobutylene.

C. Substituted Silylium Cations

In another preferred embodiment, substituted silylium compositions,preferably trisubstituted silylium compositions are combined with NCA'sto polymerize monomers. Preferred silylium cations are those representedby the formula: ##STR9## wherein R₁, R₂ and R₃ are independentlyhydrogen, a linear, aromatic or aliphatic group, provided that only oneof R₁, R₂ and R₃ is hydrogen, preferably none of R₁, R₂ and R₃ ishydrogen. Preferred aromatics include phenyl, toluyl, xylyl, biphenyland the like. Preferred aliphatics include methyl, ethyl, propyl, butyl,pentyl, hexyl, octyl, nonyl, decyl, dodecyl, 3-methylpentyl,3,5,5-trimethylhexyl and the like. In a particularly preferredembodiment R₁, R₂ and R₃ are C₁ to C₂₀ aromatic or aliphatic groups,with C₁ to C₈ alkyls being especially preferred. Preferred examplesinclude trimethylsilylium, triethylsilylium, benzyl-dimethylsilylium,and the like.

D. Composition Capable of Generating a Proton

A fourth source for the cation is any compound that will produce aproton when combined with the non-coordinating anion or a compositioncontaining a non-coordinating anion. Protons may be generated from thereaction of a stable carbocation salt which contains a non-coordinating,non-nucleophilic anion with water, alcohol or phenol present to producethe proton and the corresponding by-product, (ether in the case of analcohol or phenol and alcohol in the case of water). Such reaction maybe preferred in the event that the reaction of the carbocation salt isfaster with the protonated additive as compared with its reaction withthe olefin. Other proton generating reactants include thiols, carboxylicacids, and the like. Similar chemistries may be realized with silyliumtype catalysts. In another embodiment, when low molecular weight polymerproduct is desired an aliphatic or aromatic alcohol may be added toinhibit the polymerization.

Another method to generate a proton comprises combining a Group 1 orGroup 2 metal cation, preferably lithium, with water, preferably in awet, non-protic organic solvent, in the presence of a Lewis base thatdoes not interfere with polymerization. A wet solvent is defined to be ahydrocarbon solvent partially or fully saturated with water. It has beenobserved that when a Lewis base , such as isobutylene, is present withthe Group 1 or 2 metal cation and the water, a proton is generated. In apreferred embodiment the non-coordinating anion is also present in the"wet" solvent such that active catalyst is generated when the Group 1 or2 metal cation is added.

E. Germanium, Tin and Lead Compositions

Another preferred source for the cation is substituted germanium, tin orlead cations. Preferred examples include substances that are representedby the formula: ##STR10## wherein R₁, R₂ and R₃ are independentlyhydrogen, or a linear, branched or cyclic aromatic or aliphatic groups,preferably a C₁ to C₂₀ aromatic or aliphatic group, provided that onlyone of R₁, R₂ or R₃ may be hydrogen and M is germanium, tin or lead. Ina preferred embodiment none of R₁, R₂ or R₃ are H. Preferred aromaticsinclude phenyl, toluyl, xylyl, biphenyl and the like. Preferredaliphatics include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl,nonyl, decyl, dodecyl, 3-methylpentyl, 3,5,5-trimethylhexyl and thelike.

Active Catalyst System

A. Cyclopentadienyl Transition Metal Compounds

The Cp transition metal cations (CpTm⁺) can be combined into an activecatalyst in at least two ways. A first method is to combine a compoundcomprising the CpTm⁺ with a second compound comprising the NCA whichthen react to form a by product and the active "non-coordinating" pair.Likewise, the CpTm⁺ compound may also be directly combined with the NCAto form the active catalyst system. Typically the NCA is combined withthe cation/cation source in ratios of 1 to 1, however ratios of 1 to 100(CpTm⁺ to NCA) also work in the practice of this invention.

Active cationic catalysts can be prepared by reacting a transition metalcompound with some neutral Lewis acids, such as B(C₆ F₅)_(3n), whichupon reaction with a hydrolyzable ligand (X) of the transition metalcompound forms an anion, such as ([B(C₆ F₅)₃ (X)]⁻), which stabilizesthe cationic transition metal species generated by the reaction.

A novel aspect of this invention is the active carbocationic catalystcomplex which is formed and which can be represented by the formulae:##STR11## wherein each G is independently hydrogen or an aromatic oraliphatic group, preferably a C₁ to C₁₀₀ aliphatic group, and g is aninteger representing the number of monomer units incorporated into thegrowing polymer chain, g is preferably a number greater than or equal to1, preferably a number from 1 to about 150,000. NCA⁻ is anynon-coordinating anion as described above. All other symbols are asdefined above.

A particularly novel aspect of this invention is an active catalystcomposition that polymerizes both cationically and by coordinationmechanism. In polymerization environment containing both coordinationmonomer and cationic monomer, as defined below, it has been found that aportion of the active catalyst acts as cationic catalyst and polymerizesthe cationic monomer, a second portion of the catalyst acts acoordination catalyst and polymerizes coordination monomer, and a thirdportion of the catalyst polymerizes both cationic monomer andcoordination monomer, apparently at two sites on the same growingpolymer chain to produce copolymers, preferably block copolymers. Sinceblock copolymers are produced, it appears that there is an intermediatecatalyst structure between those that polymerize solely by cationicmechanism and those that polymerize solely by coordination mechanism. Ithas also been discovered that these cyclopentadienyl derivative NCAcatalyst systems can be triggered to polymerize by a selected mechanism,i.e. cationic or coordination, by combining them with a cationic monomeror a coordination monomer, respectively.

In another embodiment this invention also provides active catalystcompositions which can be represented by the formulae: ##STR12## whereineach G is independently a aliphatic or aromatic group, preferably a C₁to C₁₀₀ aliphatic or aromatic group, and g is a n integer representingthe number of monomer units incorporated into the growing polymer chain,g is preferably a number greater than or equal to 1, preferably a numberfrom 1 to about 50,000. NCA⁻ is any non-coordinating anion as describedabove. All other symbols are as defined above.

B. Substituted Carbocation and Silylium Compounds

Generation of trisubstituted carbocations and silylium cations may beperformed before use in the polymerization or in situ. Pre-formation andisolation of the cation or the stable cation salts may be accomplishedby reacting the alkali or alkaline earth metal salt of thenon-coordinating anion with the corresponding halogen of the potentialcarbocation or silylium similarly to methods known in the art. Formationof the substituted carbocations or silylium in situ occurs in a similarmanner to stable salts, but within the vessel and at the desiredtemperature of polymerization. The advantage of the latter procedure isthat it is capable of producing carbocations or silylium cationsotherwise too unstable to be handled by the first method. The cation orthe precursor to the cation is typically used in 1 to 1 ratios with theNCA, however ratios of 1 to 100 (C⁺ or Si⁺ to NCA) also work in thepractice of this invention.

A novel aspect of this invention is the active carbocationic catalystcomplex which is formed and which can be represented by the formulae:##STR13## wherein each G is independently hydrogen or a hydrocarbylgroup, preferably a C₁ to C₁₀₀ aliphatic group, and g is an integerrepresenting the number of monomer units incorporated into the growingpolymer chain, g being preferably a number greater than or equal to 1,preferably a number from 1 to about 150,000. NCA⁻ is anynon-coordinating anion as described above. All other symbols are asdefined above.

Yet another novel aspect of this invention is the active carbocationiccatalyst complex which is formed and which can be represented by theformulae: ##STR14## wherein each G is independently hydrogen or analiphatic or aromatic group, preferably a C₁ to C₁₀₀ aliphatic group,and g is an integer representing the number of monomer unitsincorporated into the growing polymer chain, g being preferably a numbergreater than or equal to 1, preferably a number from 1 to about 150,000.NCA⁻ is any non-coordinating anion as described above. All other symbolsare as defined above.

Germanium, Tin and Lead

In addition cationic compositions of germanium, tin or lead, may be usedin combination with the NCA's described herein. Preferred compositionsinclude those which are represented by the formula: ##STR15## whereinR₁, R₂ and R₃ are hydrogen, alkyl, aryl, aralkyl groups or derivativesthereof, preferably C₁ to C₃₀ alkyl, aryl, aralkyl groups or derivativesthereof, and M* is Germanium, tin or lead, provided that only one of R₁,R₂ and R₃ may hydrogen. In a preferred embodiment the R groups are a C₁to C₁₀ alkyl, preferably methyl, ethyl, propyl, or butyl. Thesecompositions are combined with the NCA in ratios of 1:1 to 1:100.

Polymerization

The catalyst systems of this invention may be active as combined or mayrequire activation prior to their use as polymerization catalysts. Forexample the cyclopentadienyl derivatives that are not in the cationicstate may be combined with a compound comprising the NCA which acts withthe cyclopentadienyl derivative to produce the active cationic catalyst.

In general, the active catalyst is combined with monomer in solution orslurry at temperatures below about 20° C., preferably below 0° C.according to the cationic polymerization processes known in the art.

Typical monomers which may be polymerized or copolymerized by thissystem include one or more of: olefins, alpha olefins, styrenic olefins,halogenated styrenic olefins, geminally substituted olefins, and othercationically polymerizable monomers, and or α-heteroatom olefins.Preferred olefins include isobutylene, isoprene, butadiene, styrene andthe like. Preferred alpha olefins include alpha olefins having 2 to 30carbon atoms, preferably 2 to 20 carbon atoms. Preferred alpha olefinsinclude ethylene, propylene, butene, pentene, hexene, heptene, octene,nonene, decene, dodecene, dodecyldocecene,3-methylpentene-1,3,5,5-trimethylhexene-1. Preferred styrenic monomersinclude unsubstituted styrene and alkyl styrenes, where the alkyl groupcontains up to about 60 carbon atoms, preferably 1 to 30 carbon atoms,even more preferably 1 to 8 carbon atoms. Examples include styrene,alpha-methyl styrene, para-chlorostyrene and para-methylstyrene and thelike. Preferred geminally substituted olefins include isobutylene,2-methylbutene, isoprene and the like. Preferred alpha-heteroatomolefins include alkyl vinyl ethers, and alkyl, alkenyl or aryl amines.Examples include methyl vinyl ether, isobutylvinyl ether, butyl vinylether, vinyl carbazole and the like.

Especially preferred monomers include isobutylene, 2-methyl-butene,2-methyl-pentene, styrene, alpha-methylstyrene, para-methylstyrene,vinyl ether, vinyl carbazole or combinations thereof. A particularlypreferred monomer combination is isobutylene combined with para-methylstyrene.

In another preferred embodiment, dienes polymerized as monomers orcomonomers using the catalysts described above. The diene may beconjugated or non-conjugated; cyclic, branched or linear, and compriseup to 100 carbon atoms, even more preferably up to 20 carbon atoms. In apreferred embodiment isobutylene is copolymerized with isoprene andoptionally a diene, preferably butadiene.

Depending on the choice of monomer and catalyst components, it ispossible for a monomer to be polymerized coordinatively or cationically.Since the selected monomers will choose the path with lower energyrequirements, an alpha-olefin might polymerize coordinatively with acyclopentadienyl transition metal/NCA combination, even at lowtemperatures, but will polymerize cationically in the presence of asilylium compound/NCA combination. While styrene is known to typicallypolymerize by cationic mechanism, it is also known to polymerize bycoordination mechanism. Thus in a situation where styrene is combinedwith the cyclopentadienyl derivative/NCA catalyst systems, thepolymerization mechanism will be determined by the temperature of thepolymerization. For Example, at temperatures of 20° C. or below themechanism will be cationic, while at temperature of 50° C. or more themechanism will be coordination.

Further when both coordination monomer and cationic monomer are presentin a polymerization zone catalyst compositions comprising thecyclopentadienyl transition metal derivatives and the NCA will producecopolymers of the coordination monomer with the cationic monomer. Hencein a preferred embodiment, a composition is produced that comprisespoly(cationic monomer), poly(coordination monomer) and copolymers of thecoordination and cationic monomers. Indeed, with the catalyst systemdescribed above it is possible to produce a reactor blend having its owninherent compatibilizer.

The polymerization reaction may be run in typical cationicpolymerization reactors and conditions known in the art at temperaturesat or below about 20° C., more preferably below about 0° C., preferablybelow about -20° C., more preferably below about -60° C.

The polymerization is typically performed in a solution phase, slurry orlow pressure reactor. The polymerization is typically complete in about10 minutes, however, may run from less than one minute to greater thanan hour. However, longer polymerization times are still within the scopeof this invention.

In a preferred embodiment, the catalyst systems described herein may beused in the process used to produce the products modified and describedin US Pat. No. 5,162,445, incorporated by reference herein.

Suitable solvents include both polar and non-polar hydrocarbons, such ashaloaromatics, hexanes and heptanes, halogenated hydrocarbons,especially chlorinated hydrocarbons, and the like. Specific examplesinclude, but are not limited to, methyl cyclohexane, ethyl cyclohexane,propyl cyclohexane, chloro-benzene, bromo-benzene, fluoro-benzene,iodo-benzene, methyl chloride, methylene chloride, ethyl chloride,propyl chloride, butyl chloride, chloroform and the like.

In a typical polymerization, a cation or cation source such asdimethylsilylmonocyclopentadienyl titanium dimethyl orbiscyclopentadienyl zirconium dichloride is combined in a polymerizationreactor with monomer and non-coordinating anion such astris(pentafluorophenyl) boron or triphenylmethyltetra(pentafluorophenyl)boron in a solvent, having up to about 5.0×10⁻³ mol/L of residual water.An optional proton scavenger may be present at concentrations equal toor less than the water concentration in the solvent. The reaction isthen allowed to run for 30 seconds to over an hour at temperatures belowthe ceiling temperature of the selected monomer(s), preferably belowabout -15° C.

In preferred embodiments, a proton scavenger is used to control theconcentration of the residual water in the solvent. As a general rule,it is preferred that when a cyclopentadienyl transition metal compoundis used that the water is present at about 1×10⁻⁴ mol/L or less. If morewater is present, a proton scavenger can be used to control the waterconcentration, but for best results, the proton scavenger concentrationshould not be greater than the water concentration. For the purposes ofthis invention and the claims thereto a proton scavenger is defined tobe a composition capable of reacting with free protons and not producinga new species of catalyst or if icataly produce a new species ofcatalyst, that catalyst is substantially inactive when compared to thecatalyst system of this invention. Preferred proton scavengers are2,6-di-tert-butylpyridine (DTBP), 4-methyl-2,6-di-tert-butyl-pyridine,1,8-bis(dimethylamino)-naphthalene or diisopropylethylamine used aloneor in combination. Additional information concerning differentscavengers useful in these systems can be found in U.S. Pat. Nos.5,153,157 and 5,241,025 which are incorporated by reference herein.

While not wishing to be bound by any theory, it is believed that thewater acts with the cation and the NCA to help form the cationiccatalyst. The amount of water preferred is dependent on the transitionmetal utilized. For example, the titanium cyclopentadienyl compoundsappear to be adversely affected by greater water concentration while biscyclopentadienyl zirconium compounds appear to be positively affected bygreater water concentration. Hence, in a preferred embodiment low waterconcentrations, such as 1×10⁻⁴ or less are used without a protonscavenger.

The process of this invention can produce polymers of cationicallypolymerizable monomers and can also polymerize traditional Zeigler-Nattapolymerizable monomers ("coordination monomers). Hence, this inventioncan be used to produce reactor blends, interpenetrating networks and thelike, of a coordination polymerized monomer and a cationicallypolymerized monomer by simply varying the reaction conditions and/or themonomers. The variety of reactor blends and interpenetrating networksthat can be produced fills a lengthy list. For the sake of brevity thefollowing table sets out some of the many monomers that can comprise theZiegler-Natta polymer(s) (Group A) and which of the many monomers cancomprise cationic polymer(s) (Group B) in a reactor blend or aninterpenetrating network.

    ______________________________________                                        Group A           Group B                                                     ______________________________________                                        C.sub.2 -C.sub.100 alpha-olefins                                                                Geminally disubstituted                                       including, but not limited olefins including, but not                         to: limited to:                                                               ethylene; isobutylene;                                                        propylene; isopentene;                                                        butene; isoheptene;                                                           pentene; isohexane;                                                           hexene isooctene;                                                             heptene isodecene;                                                            octene; isododecene;                                                          nonene; and                                                                   decene; alpha-heteroatom olefins                                              dodecene; including, but not limited                                          tetradecene; to:                                                              hexadecene; vinyl ether;                                                      octadecene; vinyl carbazole;                                                  dodecyldodecene; etc. and                                                     3-methyl-pentene-1; styrenics, including                                      3,5,5,-trimethylhexene-1; but not limited to:                                 etc. styrene;                                                                  alkyl styrene;                                                                para-alkyl styrene;                                                           alpha-methyl styrene;                                                         chloro-styrene;                                                               bromo-para-methyl styrene;                                                    and the like.                                                              ______________________________________                                    

There are many possible choices of cation/NCA pairs and/or reactionconditions that will produce the desired reactor blends orinterpenetrating networks. One simple, non-limiting example of the manychoices is selecting a biscyclopentadienyl transition metal compoundsuch as biscyclopentadienyl zirconium dimethyl andtriphenylmethyl-perfluorophenyl boron as the catalyst system thencontacting this system in a solvent with a cationically polymerizablemonomer ("cationic monomer") such as isobutylene (at -20° C., forexample) then adding solvent with residual water and coordinationmonomer (as defined above) such as ethylene to the reactor. Theresulting product will then be a reactor blend of polyethylene andpolyisobutylene. Likewise, if the timing or flow is altered such thatthe monomer, such as ethylene or isobutylene, is polymerized into"blocks," blends of block copolymers can also achieved.

Many of the above combinations and processes will also benefit from theability to use mixed monomer feeds. "Coordination" and "cationic"monomer can now be fed into the reactor in one stream and selectivelypolymerized by varying the reaction conditions, such as the catalyst,temperature and/or the amount of water present. Furthermore, asmentioned above, the cyclopentadienyl derivative catalysts can alsoproduce copolymers of coordination monomer and cationic monomer. Apreferred combination is a copolymer of isobutylene and ethylene. Othermonomers can be selected from the table above to provide a great varietyof these coordination-cationic copolymers.

In general, the cation combined with the NCA can be used to polymerizeolefins, particularly geminally disubstituted olefins, and styrenics tohigh molecular weights, such as an Mn of 10,000 or more, preferably100,000 or more.

All documents described herein, including testing procedures areincorporated by reference herein. In the following examples thematerials prepared and the procedures followed relate to specificembodiments of the broad invention and while forms of the inventionshave been illustrated and described, various modifications can be madewithout departing from the spirit and scope of this invention.Accordingly, it is not intended that the invention be limited thereby.

EXAMPLES

Molecular weight (Mw and Mn) were measured by Gel PermeationChromotography using a Waters 150 gel permeation chromatograph equippedwith a differential refractive index (DRI) detector. The numericalanalyses were performed using the commercially available standard GelPermeation Chromotography package, run on an HP1000 computer.

Example 1

Polymerizations were carried out under nitrogen in anhydrous solventseither directly as purchased or prepared in the laboratory by techniquesknown to those of ordinary skill in the art. Isobutylene was dissolvedinto a solvent(s) at -20° C. along with proton scavenger (DTBP)di-tert-butyl-pyridine in some polymerizations before adding thecatalyst with stirring. The catalyst was prepared by separatelydissolving each component in a solvent of choice and mixing themtogether. The resulting solution was immediately introduced into thepolymerization vessel. Polymerizations were run for a predetermined timeand were quenched with methanol addition. Product polymer was isolatedby precipitation into methanol. The basic recipe for the polymerizationincluded 10 ml of solvent(s), 10 ml of isobutylene and 4.4×10⁻⁵ moles ofthe catalyst. The catalyst was introduced in approximately 5 to 8 ml ofadditional solvent.

A) Polymerization with a Monocyclopentadienyl Derivative and aNon-coordinating Anion

The polymerizations were run according to the procedure described above.The individual run conditions are reported in Table 1 and the resultsare reported in Table 2.

                  TABLE 1                                                         ______________________________________                                               Cp*TiMe.sub.3                                                                           B(pfp).sub.3                                                                           DTBP           Time                                   Rxn # (mg) (mg) (μl) Solvent (min)                                       ______________________________________                                        94-4   10        32       --     Toluene 30                                     96-1 10 32 -- MCH 30                                                          96-2 -- 32 -- MCH 30                                                          96-4 10 -- -- ClBz 30                                                         97-2 -- 32 -- ClBz 30                                                         97-4 -- 22 200 ClBz 30                                                        96-3 10 32 -- ClBz 30                                                         97-1 10 32  8 ClBz 30                                                         97-3 10 22 200 ClBz 30                                                        97-6 10 22 -- ClBz/MCH 40                                                         (80/20)                                                                   97-7 10 22 -- ClBz/MCH 60                                                         (60/40)                                                                   97-8 10 22 -- ClBz/MCH 135                                                        (50/50)                                                                   97-9 10 22 -- ClBz/MCH 135                                                        (50/50)                                                                 ______________________________________                                         Solvents mixed volume to volume                                               Cp*TiMe.sub.3 1,2,3,4,5(pentamethyl)cyclopentadienyl titanium (IV)            trimethyl                                                                     B(pfp).sub.3 tris(pentafluorophenyl) boron                                    DTBP ditert-butyl-pyridine                                                    ClBz chlorobenzene                                                            MCH methylcyclohexane                                                         -- indicates an absence of this compound.                                

                  TABLE 2                                                         ______________________________________                                        Rxn #    Yield (%)     Mn      Mw/Mn                                          ______________________________________                                        94-4     13             75,000 2.3                                              96-1  0 ND ND                                                                 96-2  0 ND ND                                                                 96-4  0 ND ND                                                                 97-2 10 ND ND                                                                 97-4  0 ND ND                                                                 96-3 79  38,400 2.7                                                           97-1 77  68,800 1.76                                                          97-3 72  90,700 1.9                                                           97-6 82 108,300 1.67                                                          97-7 42 125,800 1.65                                                          97-8 56 124,500 1.60                                                          97-9 15 117,300 1.56                                                        ______________________________________                                         ND INDICATES NO DATA                                                     

B) Polymerization with a Biscyclopentadienyl Derivative and an NCA

The polymerizations were run according to the procedure above inchlorobenzene solvent. The individual conditions and data are reportedin Table 3.

                                      TABLE 3                                     __________________________________________________________________________    Isobutylene Polymerizations at -20° C. in Chlorobenzene                              [Metal] × 10.sup.3                                                             [H.sub.2 O] × 10.sup.3                                                        [DTBP] × 10.sup.3                                                              Time                                                                             Isolated                                   RXN Catalyst (mol/L) (mol/L) (mol/L) (min) Yield (%) Mn ×                                                            10.sup.3 Mw/Mn                 __________________________________________________________________________    131-3                                                                             Cp*.sub.2 ZrMe.sub.2                                                                    1.28   ND    --     45 63   132  1.8                              131-4 Cp*.sub.2 ZrMe.sub.2 1.28 ND 22.0 45  0 ND ND                           131-6 Cp*.sub.2 ZrMe.sub.2 2.55 ND -- 45 75 92 2.1                            134-1 Cp*.sub.2 ZrMe.sub.2 9.2 3.15 44.5 45 20 162.2 1.8                      135-1 Cp*.sub.2 ZrMe.sub.2 4.85 4.5 -- 45 60 141.1 1.9                        143-3 Cp*.sub.2 ZrMe.sub.2 1.28 0.03 -- 60 86 116.0 1.9                       148-2 Cp*.sub.2 ZrMe.sub.2 1.28 0.08 2.7.sup.a 120  24 147.0 1.8                                                            147-3 Cp*.sub.2 ZrMe.sub.2                                                    1.28 0.08 -- 60 37 136.1                                                     1.8                              145-5.sup.b Cp*.sub.2 ZrMe.sub.2 1.28 0.08 -- 60 13 273 2.3                   134-5 (Me.sub.2 Si(THI).sub.2)ZrMe.sub.2 1.53 3.15 -- 90 72 6.6 4.97                                                        145-1 (Me.sub.2 Si(THI).su                                                   b.2)ZrMe.sub.2 1.53 0.03                                                      -- 90 44 182.0 1.8                                                             131-5 Cp*.sub.2 HfMe.sub.2                                                    1.53 ND -- 90 44 150.0                                                       1.8                              133-1 Cp*.sub.2 HfMe.sub.2 2.53 3.15 44.5 45 trace ND ND                      144-3 Cp*.sub.2 HfMe.sub.2 1.53 0.03 -- 90 29 182 1.7                         133-3 Cp*.sub.2 HfMe.sub.2 1.53 3.15 -- 90 trace ND ND                        147-4 Cp*.sub.2 HfMe.sub.2 1.5 0.08 -- 60 83 100.3 1.82                       147-6.sup.b Cp*.sub.2 HfMe.sub.2 1.5 0.08 -- 60 47 292.1 2.2                __________________________________________________________________________     ND not determined;                                                            -- indicates that component was not present;                                  Cp cyclopentadienyl                                                           Cp* pentamethylcyclopentadienyl                                               Me methyl                                                                     THI tetrahydroindenyl                                                         DTBP 2,6 ditert-butyl pyridine                                                .sup.a isobutylene added 3 minutes after all ingredients have been added      .sup.b Temp. was -40° C.                                               Cp*.sub.2 ZrMe.sub.2 is bis(pentamethylcyclopentadienyl) zirconium            dimethyl.                                                                

Additional polymerizations were run according to the procedure listedabove, except that toluene was used as the solvent. The data andconditions are reported in Table 4

                                      TABLE 4                                     __________________________________________________________________________    Isobutylene Polymerizations at -20° C. in Toluene                                   [Cat] × 10.sup.3                                                              [H.sub.2 O] × 10.sup.3                                                        [DTBP] × 10.sup.3                                                              Time                                                                             Isolated                                     RXN Catalyst (mol/L) (mol/L) (mol/L) (min) Yield (%) Mn ×                                                          10.sup.3 Mw/Mn                   __________________________________________________________________________    153-1                                                                            Cp*.sub.2 ZrMe.sub.2                                                                    1.28  <0.1  --     45 26   96.7 2.1                                153-6 Cp*.sub.2 ZrMe.sub.2 1.28 <0.1 -- 45 10 133.9 1.68                      153-2 Cp.sub.2 HfMe.sub.2 1.47 <0.1 -- 45 56 131.4 1.89                       153-3 (Me.sub.2 Si(THI).sub.2)ZrMe.sub.2 1.56 <0.1 -- 45 18 124.1           __________________________________________________________________________                                                 1.74                              Cp cyclopentadienyl                                                           Cp* pentamethylcyclopentadienyl                                               Me methyl                                                                     THI tetrahydroindenyl                                                         -- none present                                                          

C) Polymerization with Substituted Carbocations

The Polymerizations were run according to the general proceduredescribed above except that 5 ml of isobutylene and 65 ml of methylenechloride(table 6) or chlorobenzene(table 5) (having 1.4×10⁻³ mol/L H₂ O)were mixed and cooled to -20° C. 83 mg of triphenylmethyltetrafluorophenylboron were dissolved into 2 ml of methylene chlorideand added to the first solution. Polymerization immediately ensued andwas allowed to run for 60 minutes. The polymerization was then stoppedby quenching with an excess of methanol. The data and conditions arereported in table 5 & 6.

                                      TABLE 5                                     __________________________________________________________________________    Isobutylvinylether Polymerizations at -20° C. in Chlorobenzene                      [Cat] × 10.sup.3                                                              [H.sub.2 O] × 10.sup.3                                                        [DTBP] × 10.sup.3                                                              Time                                                                             Isolated                                     RXN Catalyst (mol/L) (mol/L) (mol/L) (min) Yield (%) Mn ×                                                          10.sup.3 Mw/Mn                   __________________________________________________________________________    154-1                                                                            Cp*.sub.2 ZrMe.sub.2                                                                    1.28  0.08  --     45 85   5.4  7.69                               154-2 (Me.sub.2 Si(THI).sub.2)ZrMe.sub.2 1.56 0.08 -- 45 85 6.7 8.8                                                       155-1 Cp*.sub.2 ZrMe.sub.2                                                   1.28 0.08 3.3 90 21 28.3                                                      4.02                               155-4 Cp*.sub.2 ZrMe.sub.2 1.28 0.08 -- 90 58 3.8 4.05                        155-2 Cp.sub.2 HfMe.sub.2 1.28 0.08 -- 90 78 4.8 8.75                       __________________________________________________________________________     Cp cyclopentadienyl                                                           Cp* pentamethylcyclopentadienyl                                               Me methyl                                                                     THI tetrahydroindenyl                                                         -- none present                                                          

                                      TABLE 6                                     __________________________________________________________________________    ISOBUTYLENE POLYMERIZATIONS CATALYZED BY Ph.sub.3 C.sup.+ B(pfp).sub.4.sup    .-                                                                                [M] [Cat.] × 10.sup.3                                                             [H.sub.2 O] × 10.sup.3                                                        Time                                                                             Temp                                                                             Isolated                                              RXN mol/L mol/L mol/L (min) (° C.) Yield (%) Mn × 10.sup.3                                         Mw/Mn                                     __________________________________________________________________________    136-1                                                                             0.97                                                                              1.38  1.4   60 -20                                                                              66   24.5 2.5                                         136-2 0.32 1.38 1.4 60 -20 16 3.2 7.1                                         137-2.sup.a 0.97 1.38 1.4 60 -20 trace ND ND                                  138-1.sup.b 0.97 5.56 1.4 60 -20  4 ND ND                                     138-2.sup.c 0.97 5.56 1.4 60 -20 trace ND ND                                  140-4 0.97 5.56 ND 60 -20 61 6.3 2.1                                          143-6 6.3 1.95 0.03 60 -20 18 3.3 8.3                                         147-2 6.3 0.72 3.5 60 -20 30 9.9 2.08                                         134-2 6.3 1.3 6.3 60 -20 56 12 2.29                                           147-8 6.3 0.72 0.08 60 -40  9 41.3 1.5                                        147-1 6.3 0.72 3.5 60 -20 30 9.4 2.1                                          152-4.sup.d 6.3 1.3 0.08 60 -20 52 1.5 7.0                                    152-3.sup.e 6.3 1.3 0.08 60 -20 53 5.7 2.45                                 __________________________________________________________________________     .sup.a Ph.sub.3 COH added in 4.1 × 10.sup.-4 mol/L                      .sup.b 2,6dibutylpyridine added in 2.2 × 10.sup.-3 mol/L                .sup.c Ph.sub.3 CCL added in 1.4 × 10.sup.-3 mol/L                      .sup.d Phenol added in 2.1 × 10.sup.-3 mol/L                            .sup.e Methanol added in 1.2 × 10.sup.-3 mol/L                          ND no data                                                               

Additional polymerizations were conducted according to the procedurelisted in Example 1. The individual conditions and data are reported intable 7. All the reactions were run at -80° C., except 2-1 and 2-2 whichwere run at -20° C.

                                      TABLE 7                                     __________________________________________________________________________    Isobutylene Polymerizations initiated by R.sub.3 C.sup.+ B(pfp).sub.4.sup.             [M] × 10.sup.3                                                               [I] × 10.sup.3                                                               [Li].sup.a × 10.sup.3                                                             Isol'td                                            RXN Initiator.sup.b (mol/L) (mol/L) (mol/L) Sol.sup.c Yield (%) Mn                                                 × 10.sup.3 Mw/Mn                 __________________________________________________________________________    36-4.sup.d                                                                        TBDCC                                                                              3.8  2.0  4.3  CH.sub.2 Cl.sub.2                                                                  100  8.77 20.82                                    36-5 TBDCC 1.9 2.0 4.3 CH.sub.2 Cl.sub.2 100  87.12 10.9                      159-1 TBDCC 1.9 1.9 3.8 m60/40 96 53.7 4.8                                    159-2 TBDCC 1.9 1.9 3.8 m60/40 96 ND 47.2 5.0                                 159-3.sup.e TBDCC 1.9 1.9 3.8 m60/40 73 15.7 2.4                              159-4.sup.f TBDCC 1.9 1.9 3.8 m60/40 86 7.54 3.7                              160-1 TMPCl 1.9 1.7 1.9 m60/40 92 1980.2 2.5                                  160-2 TBDCC 1.9 1.9 3.8 m60/40 87 2.8 1.9                                     162-4.sup.g TBDCC 6.3 6.3 12.6 CH.sub.2 Cl.sub.2 81 2.18 3.3                  162-5.sup.h TBDCC 6.3 6.3 12.6 CH.sub.2 Cl.sub.2 ND ND ND                     162-6.sup.i TBDCC 6.3 6.3 12.6 CH.sub.2 Cl.sub.2 61 18.5 6.2                  164-1 TBDCC 1.9 1.9 3.8 MCH 85 67.6 2.96                                      164-2.sup.f TBDCC 1.9 1.9 3.8 MCH 28 12.5 5.0                                 2-1 PIB-2000 1.9 1.9 3.8 m60/40 94 28.0 3.3                                   2-2 TBDCC 1.9 1.9 3.8 m60/40 99 4.7 6.0                                       3-1 BzBr 2.5 1.9 2.5 CH.sub.2 Cl.sub.2 59 2313.8 2.6                          3-2 BzNO.sub.2 Br 2.5 1.9 1.9 CH.sub.2 Cl.sub.2  8 2900. 1.93                 3-3 TBDCC 1.9 1.9 7.6 MCH 100  52.2 3.8                                       3-5 TBDCC 1.8 1.8 3.75 m70/30 96 30.5 5.6                                     3-6 TBDCC 1.8 1.8 3.75 m57/43 85 ND ND                                        42-4 -- 1.9 -- 3.8 mx60:40 17 1606.7 2.0                                    __________________________________________________________________________     -- none present,                                                              ND no data available,                                                         .sup.a lithium tetraperfluorophenylboron;                                     .sup.b TBDCC  1,3bis(1-chloro-1methylethyl)-5-tert-butylbenzene, TMPCl        2chloro-2,4,4-trimethylpentane, PIB2000  α,t-chloro polyisobutylene     whose Mn is 2000, BzBr  benzyl bromide, BzNO.sub.2 Br                         --onitrobenzylbromide;                                                        .sup.c MCH = methylcyclohexane, CH.sub.2 Cl.sub.2 = methyldichloride m =      mix of (MCH)/(CH.sub.2 Cl.sub.2), numbers indicate volume percent in          solution; mx = mix of (hexanes)/(CH.sub.2 Cl.sub.2), numbers indicate         volume percent in solution                                                    .sup.d sequential addition of 5 ml of monomer after 5 minutes;                .sup.e 10 Mol % of pinene in the feed;                                        .sup.f 10 Mol % isoprene in the feed;                                         .sup.g pinene homopolymerization;                                             .sup.h 10 Mol % pmethylstyrene in the feed;                                   .sup.i sequential addition of 3 ml of pmethylstyrene after 5 minutes;         .sup.j 10 Mol % 4vinylcyclohexene in the feed.                           

The polymerizations ran for 30 to 60 minutes.

D) Polymerizations with a Substituted Silylium

The polymerizations were carried out as described above for 10 minutesand except as otherwise noted. The individual conditions and data arereported in table 8.

                                      TABLE 8                                     __________________________________________________________________________    ISOBUTYLENE POLYMERIZATIONS WITH Et.sub.3 Si.sup.+ B(pfp).sub.4.sup.-             [M] [Cat] × 10.sup.3                                                                  Temp                                                                              Isolated                                                  RXN mol/L mol/L Solvent (° C.) Yield (%) Mn × 10.sup.3                                         Mn/Mw                                         __________________________________________________________________________    120-1                                                                             6.3 11.0  MCH -20 54   700  2.7                                             120-2 6.3 11.0 MCH -20 48 .9 2.7                                              120-3 12.6 trace neat -20 100  21.4 3.2                                       121-1 6.3 9.4 MCH -20 ND 2.1 6.6                                              123-1 6.3 4.2 MCH -20 <1 ND ND                                                123-2 6.3 2.77 MCH -80  6 115.9 4.6                                           123-3 6.3 2.7 ClBz -45 100  5.9 13.1                                          129-1.sup.b 6.3 1.26 MP -20 73 77.8 1.75                                    __________________________________________________________________________     ND no data available,                                                         MCH methylcyclohexane                                                         ClBz chlorobenzene                                                            MP methylpropane                                                              .sup.b 5t-butyl-bis-1,3(1-chloro-1-methylethyl)benzene.                  

E) Ethylene/Isobutylene Copolymerization with CP₂ HfMe₂ & Ph₃ CB(PfP)₄

The polymerization was run at -20° C. in a stirred Parr reactor.Isobutylene (20 ml) was dissolved into 40 ml of dried, anhydrouschlorobenzene directly in the reactor. The reactor was sealed andthermostated in a both at -20° C. Separately the catalyst was preparedand activated by separately dissolving 10 milligrams of Cp₂ HfMe₂ and 19milligrams of Ph₃ CB(pfp)₄ into 2 ml of solvent each and then combiningthe solutions. The activated catalyst solution was then added to thestirred reaction vessel. Polymerization of isobutylene ensued and wasallowed to continue for a pre-determined time (T₁). The reactor was thenpressurized to 60 psi (414 kPa) with ethylene. Reactions were allowed tocontinue maintaining this pressure for a time (T₂). The reaction wasthen quenched with the addition of methanol. The polymer mass wasisolated by precipitating with methanol, washing and drying in vacuo.After analysis of Molecular Weight and composition by proton NMR, thesamples were extracted according to the schemes below.

                  TABLE 9                                                         ______________________________________                                                       [Catalyst]                                                                             [H.sub.2 O]                                                                          T.sub.1                                                                             T.sub.2                                                                             Yield                                RXN Catalyst M/L × 10.sup.4 M/L × 10.sup.3 (min) (min)                                                     (grams)                            ______________________________________                                        158-3                                                                              Cp.sub.2 HfMe.sub.2                                                                     7.6      0.08   10     4    9.78                                 158-1 Cp*.sub.2 ZrMe.sub.2 6.4 0.08 15 30 11.0                              ______________________________________                                         Cp = cyclopentadienyl                                                         Cp* = pentamethylcyclopentadienyl                                             Me = methyl                                                              

                  TABLE 10                                                        ______________________________________                                                                       1H-NMR  1H-NMR                                   RXN Mn Mw/Mn modality wt. % PIB wt. % PE                                    ______________________________________                                        158-3   9740  11.8     2       84      16                                       158-1 74,000 8.0 2 85 15                                                    ______________________________________                                    

The extraction scheme 1 for sample 158-3 was as follows.

0.6092 grams of the sample 158-3 was treated with hot methylcyclohexaneand divided into two fractions. Fraction A, the hot methylcyclohexaneinsoluble portion, was found by ¹ H-NMR to show only polyethylene peaksand comprised 12.7 wt % of the original sample. Fraction B, the hotmethylcyclohexane soluble portion, was found to show both polyethyleneand polyisobutylene ¹ H-NMR peaks and comprised 87.3 wt. % of theoriginal sample. Fraction B was then treated with room temperaturechloroform and separated into two fractions. Fraction C, the chloroforminsoluble fraction, was found to show both polyethylene andpolyisobutylene ¹ H-NMR peaks. Fraction D, the chloroform solublefraction, was found to contain only polyisobutylene ¹ H-NMR peaks. The ¹H-NMR for fraction C is FIG. 1. From these data, it is concluded thatFraction A contains polyethylene, Fraction B contains polyethylene,polyisobutylene and a copolymer of ethylene and isobutylene, Fraction Ccontains ethylene-isobutylene copolymer and fraction D containspolyisobutylene.

The extraction scheme for samples 158-3 and 158-1, performed separatelywas as follows:

The crude sample was treated to hot hexanes. The hot hexane insolubleportion, Fraction 1, was found by ¹ H-NMR to show only polyethylenesignals. The hot hexanes soluble portion, Fraction 2, was found by ¹H-NMR to show both polyethylene and polyisobutylene signals. Fraction 1was then further subjected to hot methylcyclohexane. Both the insolubleportion and the soluble portion, Fractions 3 and 5 respectively, werefound by ¹ H-NMR to show only polyethylene signals. Fraction 2 wassubjected to room temperature hexane (room temperature chloroform couldbe substituted here). The hexane(/chloroform) insoluble portion,Fraction 4, was found by ¹ H-NMR to show both polyethylene andpolyisobutylene signals. The hexane/chloroform soluble portion, Fraction6, was found to only show polyisobutylene signals. FIG. 2 is the ¹ H-NMRfor Fraction 4. Further information about the extraction is presented intable 11.

                                      TABLE 11                                    __________________________________________________________________________    Fraction 3   Fraction 4                                                                            Fraction 5                                                                            Fraction 6                                       Sample                                                                            Wt. %                                                                              Pol*.                                                                             Wt. %                                                                             Pol*.                                                                             Wt. %                                                                             Pol*.                                                                             Wt. %                                                                             Pol*.                                        __________________________________________________________________________    158-3                                                                             1.7  PE  1.3 PE, 19  PE  78  PIB                                                PIB-PE                                                                    158-1 17.2 PE 0 0 11.6 PE 71.2 PIB                                          __________________________________________________________________________     Pol*. = polymers present in the fraction.                                

Discussion

This invention demonstrates that many new, and heretofore unknown,carbocationic polymerization possibilities exist, including combining areactive cationic source such as a metallocene with a non-coordinatinganion and obtaining a combination capable of initiating cationicpolymerization of olefins. Since polymer molecular weight andpolymerization attributes are typically dependent upon the nature of thereactive cation source in a cationic polymerization, this invention alsoprovides new methods to obtain new combinations of good molecular weightwith other polymerization attributes, such as, but not limited to,yield, molecular weight distribution, conversion and the like. Thesecombinations were not possible with the traditional Lewis acid basedsystems.

Cationic polymerization of isobutylene and other cationicallypolymerizable monomers, such as isobutylvinylether, via transition metalderivatives and non-coordinating anions is demonstrated in Tables 1, 2,3, 4 and 5. (This form of initiation can also be extended to othertraditional cationic monomers described in H.-G. Elias in Macromolecules(Plenum Press, 1984, Vol. 2, p. 641f.)) Furthermore, not only do thesecatalyst systems polymerize cationically, they are also capable ofgenerating unexpectedly high molecular weight polyisobutylenes attemperatures higher than typically used for known Lewis acid systems.Note that polymerizations in Table 4 are run at -20° C. yet still obtainexcellent number average and weight average molecular weights (M_(w)=M_(n) ×M_(w) /M_(n)). Few other catalysts can obtain this performanceat this temperature. See J. P. Kennedy in Cationic Polymerization ofOlefins: A Critical Inventory (J. Wiley & Sons, 1975, p. 130, et seq.)for evidence that demonstrates that few other catalysts exceed theperformance of this invention. Furthermore, few of these known catalystsfound in Kennedy's book are homogenous and as chemically simple as thisinvention.

As previously indicated, controlled polymerizations of monomers onlycapable of cationic polymerization, have not previously been catalyzedby monocyclopentadienyl or biscyclopentadienyl transition metalderivatives alone or in combination with an activator. The use of thenon-coordinating anion with the transition metal derivative makescationic polymerization possible from these typical coordinationcatalysts. The biscyclopentadienyl transition metal compounds used inthis invention are known to catalyze the coordination polymerization ofolefin monomers like ethylene. Ethylene, however, is a poor cationicmonomer and is not expected to polymerize cationically in the presenceof these catalysts. Since the ability of these catalysts to polymerizeisobutylene and isobutylvinylether, traditional cationic monomers, hasbeen demonstrated, the duality of these catalysts toward both cationicand coordination polymerization has been revealed. Thus, provided thatappropriate conditions are used for the selected monomer set, it ispossible for one catalyst to polymerize both monomer types in onereactor. Furthermore depending on the catalyst and conditions selected,blends or copolymers of the two different classes of monomers can bemade.

One of the many facets of the dual nature of a preferred embodiment ofthis invention is demonstrated in Tables 9, 10 and 11 where a copolymerof ethylene and isobutylene is shown. Evidence that a copolymer ofethylene and isobutylene has been produced is provided by solventextraction data. Extraction and analysis of the products indicatewhether a blend or a copolymer or a mixture of the two is preparedduring a reaction. The data presented here indicate that both blends andcopolymer formation are possible. This accomplishment has beenheretofore unknown.

This invention also demonstrates that proton initiation of cationicmonomer polymerization by action of a stable cation salt of a Lewis acidmetal halide with a proton source, such as water, alcohols, etc. ispossible when the stable cation salt contains a non-coordinating anionas is demonstrated in Table 6. While, reactions of water with stablecation salts are known (A. Ledwith and D. C. Sherrington, Adv. Polym.Sci., 19, 1(1973), they are not known to lead to the polymerization ofisobutylene. This invention's use of a non-coordinating anion permitsinitiation of isobutylene from a water borne proton thus providing thekey element necessary for making this reaction an initiation step forisobutylene polymerization. This conclusion is supported by the data inExperiments 136-1, 136-2, and 143-6, 147-2, 134-2 which demonstrate thatan increase in monomer concentration or water concentration increasesthe overall yield. This indicates that both "water" and monomer arebeing consumed in the polymerization reaction. Experiments 137-2 and138-2 demonstrate that increasing the byproduct concentration (Ph₃ COH)or introducing a common salt (Ph₃ CCl) with poorer dissociativeproperties, inhibits the initiation of isobutylene, i.e. the by productdrives the equilibrium to the left tying up more of the protons so thatless of NCA is balanced with a free proton. Thus proton initiation of acationic polymerization is now possible by using the non-coordinatinganions as described herein.

In addition this invention also provides for a method to initiatecationic polymerization by in situ formation of a carbocationicinitiation site. For example, reaction of the lithium salt of the NCAwith an active organic halide (defined as one that will provide arelatively stable carbocation such as benzylic, allylic, t-alkyl, etc.)will produce an active catalyst site that will polymerize cationicmonomers. Similar reactions to cause initiation of carbocationicpolymerization by reacting an organic halide with a metal salt of aLewis acid metal halide are known, however, the reaction is usually apoor initiator providing poor yields unless a silver salt of the Lewisacid salt is used (e.g. AgBF₄). Silver salts were used to ensurecomplete reaction by the precipitation of the silver halide (usuallychloride or bromide) salt. Likewise, lower metal salts, like alkali andalkaline earth's, are generally incapable of providing complete reactionfor initiation. This is especially the case for lithium salts. Thus itis unexpected to find that the lithium salt of a NCA is so efficient atcausing initiation of isobutylene polymerization using this technique.Indeed in most cases, yields obtained using the lithium salt/NCAcombination are quite high and molecular weight over the entire spectrumcan be prepared by selecting solvent and temperature conditions as wellas the concentrations of monomer and the two components of the initiator(organic halide and lithium salt of the NCA).

Finally, Table 8 demonstrates yet another method to initiate cationicpolymerization using NCA's. In Table 8 the NCA concept is applied toinitiation from silylium salts. Relatively stable silylium salts arerelatively new chemical compounds (C&EN, Nov. 8, 1993, p.41) and it isunexpected that these salts will polymerize olefins. This inventionhowever provides a silylium composition that catalyzes a virtuallyterminationless polymerization. When combined with NCA's the silyliumsalts in polar solvents or in neat isobutylene, these polymerizationsare "terminationless" as defined by D. C. Pepper and P. J. Reilly forstyrene polymerization (Proced. Royal Soc. Chem., Ser. A, .291, 41(1966)). In other words, once the first monomer charge is consumed,further addition of monomer continues the polymerization and results incomplete consumption of the second batch. This process may be continueduntil either a contamination is brought into the reactor or the reactionis purposefully quenched. A terminationless polymerization catalystsystem for cationic monomers, particularly isobutylene polymerizationhas not been previously known.

All documents described herein are incorporated by reference herein. Asis apparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby.

I claim:
 1. A process for the polymerization of cationicallypolymerizable olefins comprising contacting under polymerizationconditions one or more olefins with a catalyst comprising:a cation, anda compatible non-coordinating anion. wherein said cation is selectedfrom the compounds represented by the following formula: ##STR16##wherein M is germanium, tin or lead, and R₁, R₂ and R₃ are independentlyhydrogen, or linear, branched or cyclic aromatic or aliphatic groups,provided that only one of R₁, R₂ or R₃ may be hydrogen.
 2. The processof claim 1 wherein the compatible non-coordinating anion istriphenylmethyltetraperfluorophenylboron or tris(pentafluorophenyl)boron.
 3. The process of claim 1 further comprising a proton scavenger.4. The process of claim 3 wherein the proton scavenger is one of2-6-di-tert-butylpyridine, 4-methyl-2,6-di-tert-butyl-pyridine,1,8-bis(dimethylamino)-naphthalene, diisopropylethylamine or mixturesthereof.
 5. The process of claim 1 wherein the ratio of number of molesof cation source to the number moles of non-coordinating anions is about1 to
 1. 6. The process of claim 1 wherein the polymerization conditionscomprise a temperature of less than 0° C.
 7. The process of claim 1wherein the polymerization conditions comprise a temperature of -30° C.or less.
 8. The process of claim 1 wherein the polymerization conditionscomprise a temperature less than about -60° C.
 9. The process of claim 1wherein the olefin comprises two different cationically polymerizableolefins.
 10. The process of claim 1 wherein the olefin is geminallysubstituted.
 11. The process of claim 10 wherein the olefin comprisesisobutylene.
 12. The process of claim 1 wherein each R group has 1 to 8carbon atoms.
 13. A process for the polymerization of cationicallypolymerizable olefins comprising contacting under polymerizationconditions one or more olefins with a catalyst comprising:a cation, anda compatible non-coordinating anion, wherein said cation is representedby the formula: ##STR17## wherein R₁, R₂ and R₃ are independentlyhydrogen, or linear, branched or cyclic aromatic or aliphatic groups,provided that only one of R₁, R₂ or R₃ may be hydrogen.
 14. The processof claim 13 wherein the compatible non-coordinating anion istriphenylmethyltetraperfluorophenylboron or tris(pentafluorophenyl)boron.
 15. The process of claim 13 further comprising a protonscavenger.
 16. The process of claim 14 wherein the proton scavenger isone of 2-6-di-tert-butylpyridine, 4-methyl-2,6-di-tert-butyl-pyridine,1,8-bis(dimethylamino)-naphthalene, diisopropylethylamine or mixturesthereof.
 17. The process of claim 13 wherein the ratio of number ofmoles of cation source to the number moles of non-coordinating anions isabout 1 to
 1. 18. The process of claim 13 wherein the polymerizationconditions comprise a temperature of less than 0° C.
 19. The process ofclaim 13 wherein the polymerization conditions comprise a temperature of-30° C. or less.
 20. The process of claim 13 wherein the polymerizationconditions comprise a temperature less than about -60 ° C.
 21. Theprocess of claim 13 wherein the olefin comprises two differentcationically polymerizable olefins.
 22. The process of claim 13 whereinthe olefin is geminally substituted.
 23. The process of claim 22 whereinthe olefin comprises isobutylene.
 24. The process of claim 13 whereineach R group has 1 to 8 carbon atoms.
 25. A process for thepolymerization of cationically polymerizable olefins comprisingcontacting under polymerization conditions one or more olefins with acatalyst comprising:a cation represented by the formula: ##STR18##wherein R₁, R₂ and R₃ are independently hydrogen, or linear, branched orcyclic aromatic or aliphatic groups, provided that only one of R₁, R₂ orR₃ may be hydrogen; and a compatible non-coordinating anion representedby the formula:

    [(M').sup.m+ Q.sub.1 . . . Q.sub.n ].sup.d-

wherein: M' is a metal or metalloid; d is an integer greater than orequal to 1; Q₁ to Q_(n) are, independently, bridged or unbridged hydrideradicals, dialkylamido radicals, alkoxide and aryloxide radicals,hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl andsubstituted-halocarbyl radicals and hydrocarbyl andhalocarbyl-substituted organometalloid radicals and any one, but notmore than one of Q₁ to Q_(n) may be a halide radical; m is an integerrepresenting the formal valence charge of M; and n is the total numberof ligands Q.
 26. The process of claim 25 wherein each R group has 1 to8 carbon atoms.
 27. The process of claim 25 wherein the compatiblenon-coordinating anion is triphenylmethyltetraperfluorophenylboron ortris(pentafluorophenyl) boron.
 28. The process of claim 25 furthercomprising a proton scavenger.
 29. The process of claim 28 wherein theproton scavenger is one of 2,6-di-tert-butylpyridiene,4-methyl-2,6-di-tert-butyl-pyridine, 1,8-bis(dimethylamino)-naphthalene,diisopropylethylamine or mixtures thereof.
 30. The process of claim 25wherein the polymerization conditions comprise a temperature less thanabout -60° C.
 31. The process of claim 25 wherein the ratio of number ofmoles of cation source to the number moles of non-coordinating anions isabout 1 to
 1. 32. The process of claim 25 wherein the polymerizationconditions comprise a temperature of less than 0° C.
 33. The process ofclaim 25 wherein the polymerization conditions comprise a temperature of-30° C. or less.
 34. The process of claim 25 wherein the olefin isgeminally substituted.
 35. The process of claim 25 wherein the olefincomprises two different cationically polymerizable olefins.
 36. Theprocess of claim 25 wherein the olefin comprises isobutylene.